Search results for "ROV"
showing 10 items of 5770 documents
BacSr1−cTiO3 perovskite solid solutions: Thermodynamics from ab initio electronic structure calculations
2005
We suggest theoretical prediction for Ba"cSr"1"-"cTiO"3 perovskite solid solutions (BST) combining ab initio DFT/B3PW calculations and alloy thermodynamics. This approach is based on calculations of a series of ordered super-structures in Ba-Sr simple cubic sublattice immersed in the rest TiO"3 matrix. Although these structures are unstable with respect to the decomposition, the results of total energy calculations allow us to extract the necessary energy parameters and to calculate the phase diagram for the solid solutions (alloys). A novel approach applied to the BST system enables to predict that at T>400 K Ba and Sr atom distribution is random. But below this temperature at small c Ba a…
Synthesis of Uvarovite Garnet
1989
A garnet with interesting optical properties is synthesized by means of the ceramic method and the formation of gels. Colloidal silica or tetraethoxysilane (TEOS) is used as a starting reagent in the latter method of synthesis, together with nitrate and chloride salts of the remaining components. Use is made of ultraviolet-visible and infrared spectroscopy techniques and X-ray diffraction in studying the evolution of the system. Formation of the garnet phase at lower temperatures is observed when using the gel methods, as well as the absence of chromates during the process in the samples which contained chlorides.
Understanding the mechanism of the Povarov reaction. A DFT study
2014
The molecular mechanism of the Povarov reaction in acetonitrile has been studied at the MPWB1K/6-311G** level of theory. This reaction follows a domino process that comprises two sequential reactions: (i) a Lewis acid catalysed aza-Diels–Alder (A-DA) reaction between a N-aryl imine and a nucleophilic ethylene yielding a formal [4 + 2] cycloadduct; (ii) a stepwise 1,3-hydrogen shift at this intermediate affording the final tetrahydroquinoline. At this computational level, the Lewis acid catalysed A-DA reaction presents a two-step mechanism as a consequence of the large stabilisation of the corresponding zwitterionic intermediate. Our study allows establishing that the N-aryl substituent has …
ChemInform Abstract: Gold-Catalyzed Povarov-Type Reaction of Fluorinated Imino Esters and Furans.
2016
A gold-catalyzed Povarov-type reaction of fluorinated imino esters and furans is described. The process, which takes place in dichoromethane at room temperature, gives rise to novel fluorinated tetrahydrofuran-fused tetrahydroquinolines in good yields and moderate levels of diastereoselectivity in a very simple manner. The reported examples expand the versatility of the Povarov reaction to unprecedented fluorinated substrates, generating scaffolds that contain quaternary α-amino acid units.
Hansen theory applied to the identification of nonhazardous solvents for hybrid perovskite thin-films processing
2018
Abstract Metal-halide perovskites have become the most studied material for efficient next-generation solar cells, in part because of the possibility of depositing high quality semiconducting perovskites by simple solution-based methods. However, the majority of solvent systems implemented in literature for deposition of lead halide perovskites are hazardous to handle. Investigation of alternatives perovskite processing methods are hence key to safely upscale the perovskite photovoltaic manufacturing. In this manuscript we use the Hansen theory to find suitable nonhazardous solvents to solubilize two lead salts, PbBr2 and PbI2, used to fabricate the corresponding methylammonium (MA) lead ha…
Anion ordering and defect structure in Ruddlesden-Popper strontium niobium oxynitrides
2004
The crystal structure of the n = 1 member of the Ruddlesden-Popper family (SrO)(SrNbO(2)N)(n) was refined by the Rietveld method using neutron powder diffraction data. This complex crystallizes in the I4/mmm space group with cell parameters a = 4.0506(2) and c = 12.5936(9) angstroms. The refined composition was Sr(2)NbO(3.28)N(0.72), which corresponds to a formal oxidation state for Nb of +4.72, meaning 72% Nb(V) and 28% Nb(IV). The nitrogen atoms order in the equatorial sites of the niobium octahedra according to Pauling's second crystal rule as the more charged anion occupies the site showing the larger bond strength sums. Pauling's second crystal rule is shown to be able to predict the d…
A DFT study of the mechanism of Brønsted acid catalysed Povarov reactions
2015
Abstract The molecular mechanism of the Bronsted acid (BA) catalysed Povarov reaction of N -phenyl- C -methoxycarbonyl imine with a methylenecyclopropane (MCP) has been investigated using DFT methods at the MPWB1K/6-31G(d) level. This BA catalysed Povarov reaction is a domino process initialised by the formation of a cationic intermediate which experiences a quick intramolecular Friedel–Crafts reaction yielding the final tetrahydroquinoline. Protonation of the imine nitrogen atom notably increases the electrophilicity of the corresponding species, accelerating the reaction through ionic processes. Analysis of the Parr functions in the initial nucleophilic attack of MCP to the protonated imi…
Semi-empirical simulations of surface relaxation for perovskite titanates
2000
The (100) and (110) surface relaxations are calculated for SrTiO 3 and BaTiO 3 perovskite thin films. By means of a semi-empirical shell model, the positions of atoms in 16 near-surface layers placed atop a slab of rigid ions are calculated. Surface rumpling and surface-induced dipole moments are calculated for all possible surface terminations. Our results for the (100) surface structure are in good agreement with ab-initio plane-wave pseudopotential calculations and LEED experiments. The surface energy for the Ba-, Sr-, TiO-terminated (110) surfaces is found to be much larger than that for the (100) surface. In contrast, the surface energy for the asymmetric O termination, where outermost…
Rotation correlation time as a measure of microviscosity of excited state isomerization reactions of three cyanine dyes in n-alcohol solutions
1994
Abstract Rotation correlation times of three chemically similar cyanine dyes of different sizes in n -alcohol solutions have been recorded at several temperatures by using polarized picosecond spectroscopy. For all three dyes the linear temperature dependencies of τ or on η/ T were observed to be independent of solvent up to viscosities of about 60 cP. The rotational motion of the dyes proceeds at much slower rates than the excited state isomerization in viscous solutions of the same fluidity. Isomerization seems to depend on special solvent-induced changes of the force field of the reactant and clearly proceeds faster, especially for the two larger dyes, than predicted by Kramers' theory a…
Electromechanical Properties of Ba(1–x)SrxTiO3 Perovskite Solid Solutions from First-Principles Calculations
2017
Many thanks to M. Maček-Kržmanc, R. A. Evarestov, D. Gryaznov and D. Fuks for fruitful discussions. This study was supported by the ERA-NET HarvEnPiez project.